N,n-disubstituted amides



United States Patent Office 3,515,754 Patented June 2, 1970 U.S. Cl. 260558 1 Claim ABSTRACT OF THE DISCLOSURE This invention relates to N,N-disubstituted amides which are useful as hydrophobic and hydrophilic resin plasticizers.

This application is a division of SN. 632,464, filed Dec. 16, 1966.

A nonexclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to N,N-disubstituted amides. More specifically, it relates to N,N-disubstituted amides useful as primary plasticisers for hydrophobic and hydrophilic resins. Still more specifically, it relates to vinyltype resin compositions comprising the N,N-disubstituted amide plasticisers. These plasticisers are characterized by their great efiiciency as compatible plasticisers for polyvinyl thioride polymers and copolymers imparting desirable low temperature properties and low volatility loss to the plasticised resin.

A primary object of the present invention is to provide for vinyl-type hydrophobic resins a group of primary plasticisers that are highly compatible with and do not exude from those resins.

Another object is to employ as these plasticisers certain novel N,N-disubstituted amides. Still another object is to prepare these N,N-disubstituted amides from commercially-available chemicals using commercially-available equipment. A still further object is to provide a plasticised vinyl-type polymer or copolymer comprising these plasticisers. These and other objects Will be discussed more fully below.

The N,N-disubstituted amides may be represented by the formula CH2) n'X R --N (C H2) n-X wherein:

is an acyl group having from 8 to 22 carbon atoms and may be saturated, unsaturated, normal, branched, epoxy, aliphatic, cyclic, alicyclic, naphthenic, terpenic, tarpene-derived, and mixtures thereof,

(b) n is an integer equal to at least one but less than five, that is, from 1 to 4 inclusive, and (c) X is a member selected from the group consisting OR -COOR' CN O(CH CN 0 (CH COOR' wherein R is an alkyl group containing from one to eight carbon atoms, and (d) m is one or two.

Among the operable N,N-disubstituted amides of this invention are compounds of the above general formula in which the acyl group,

is an acyl such as the .acyls of the following types of acids: monobasic and dibasic normal or branched chain alkanoic and alkanoic acids with substituents in the chain such as; dichlorostearic acid; monoor dihydroxystearic acids; acyloxyacids such as 12-acetoxyoleic, 12-acetoxystea-ric, 9,10-diacetoxystearic, and acylated recinoleic acids and the like; 12-beta-cyanoethoxyo1eic and 12-cyanoethoxystearic acids and the like; recinoleic acid; phenylstearic acid; phenoxystearic acid; mono-, di,- or triepoxy stearic acids; monoor diepoxy oleic acid; epoxydocosanoic acid; dimerised or trimerised linolenic, linoleic, or oleic acid; etc.; cyclic or alicyclic acids such as cyclized linoleic and/or linolenic acids; Diels-Alder adducts of such individual or mixed polyenoic acids as can be derived from tung oil acids or soybean acids; the Diels- Alder adducts of individual or mixed tung oil acids with di-alkyl maleates, alkyl acrylates, acrylonitrile, fomaro nitrile and the like; tall oil acids; resin-derived or terpenederived acids such as abietic, l-pimaric, pinomic and the gamma-lactone of beta-hydroxyisopropyl pinolic acid; as well as the mono-alkyl esters of dibasic acids such as the monobutyl esters of pinic, adipic, sebacic, azelaic, brassylic, carboxystearic, phthalic, and terephthalic acids, or of phosphonated fatty acids such as dialkyl phosphonostearic acid, and the like.

Also included among the operable N-acyl compounds of this invention are the corresponding N,N-disubstituted amides of normal, branched, aliphatic, alicyclic, or aromatic dibasic acids such as adipic, sebacic, azelaic, brassylic, carboxystearic, dimer, trimer, pinic, phthalic, and terephthalic acids. Other useful binary, ternary or multiple component mixtures of amides of saturated, monounsaturated, and polyunsaturated acids are the N,N-disubstituted amides of synthetic mixtures of fatty acids which can be obtained from such natural sources as white greases, menhaden oil, jojoba oil, parsley seed oil, rapeseed oil, crambe seed oil, cottonseed oil, soybean oil, Limnanthes douglasii seed oil, palm oil, Vernonia anthalmintica seed oil, castor oil, and other seed oils; or from foote, tall-oil acids or resin acids.

As used herein, the term dimer Acid or dimarized acid relates to acids or mixtures of acids consisting essentially of dibasic acids containing from 32 to 44 carbon atoms resulting from polymerization or dimerization of 3 long chain C to C unsaturated fatty acids. The term trimer acid, or trimerized acids relates to acids or mixtures of acids consisting essentially of tribasic acids containing from 48 to 66 carbon atoms resulting from the polymerization or trimerization of long chain C to C unsaturated fatty acids. These products are commercially available.

Specific examples of the N,N-disubstituted amides described above are:

N,N-bis(2-methoxyethyl)oleamide N,N-bis(2-ethoxyethyl)oleiamide N,N-bis(2-ethoxyethyl)palmitamide N,N-bis(2-ethoxyethyl)-2-ethylhexaneamide N,N-1bis(2-ethoxyethyl)naphthenamide Ethyl 2,2-dimethyl-3-[di(2-methoxyethyl)amino1carbonylcyclobutaneacetate N,N-bis(Z-methoxyethyDamide of hydrogenated cottonseed oil fatty acids N,N- bis(2-ethoxyethyl)amide of animal acids N,N-bis(2-cyanoethyl)oleamide N,N-bis(2-ethoxyethyl)decanamide N,N-ibis 2-ethoxyethyl) stearamide N,N-bis 2-ethoxyethyl) arucamide N,N-bis(2-ethoxyethyl)amide of Limnanthes .douglasall oil fatty acids N,N,N',N'-tetra(2-ethoxyethyl)amide of dimer acid N,N-bis(2-methoxyethyl)amide if parsley seed oil fatty acids N,N-bis(2-methoxyethyl)amide or rapeseed oil fatty acids N,N-bis(2-methoxyethyl)linoleamide N,N-bis Z-ethoxyethyl epoxystearamide N,N-bis(Z-cyanoethoxyethyl)oleamide N,N-bis carbethoxymethyl) oleamide It is an advantage of our invention that the N,N-disubstituted amides are excellent primary, solvent-type plasticisers for vinyl-type resins. As used herein, the term primary, solvent-type plasticizer relates to a compound which is compatible when used alone. The term vinyl-type resin includes the hydrophobic polymers and copolymers of monomers containing vinyl chloride in major proportions by weight.

It is a further advantage of our invention that the N,N-disubstituted amides are compatible, solvent-type plasticizers for the vinyl-type resins. As used herein, the terms compatible, good compatibility, and compatible plasticizers refer to plasticizers which show no sign of exudation or migration to the surface for at least two weeks during shelf storage, when the plasticizers are present in the hydrophobic resin in proportions of about 70 parts of plasticizer per 100 parts of resin, parts being by weight. When a resin is plasticized with a compound with which it has only limited compatibility, the plasticizer soon exudes or migrates to the surface unless the plasticizer is used either in a limited amount or is used in conjunction with a mutual solvent (a compatible auxiliary plasticizer) to obtain adequate compatibility.

It is a still further advantage of this invention that the eflicient, primary, solvent-type plasticizers may be made from commercially-available, low-price fatty acids using commercially-available equipment. Most important these novel plasticizers for vinyl-type resins are characterized by excellent low-temperature properties, i.e., they prevent the resin composition from becoming brittle or from cracking at sub-zero centigrade temperatures.

These N,N-disubstituted amides may also be used as softeners for nitrile rubber, e.g. Hycar 1042 (33% acrylonitrile).

These and other advantages will be apparent to those skilled in the art.

The compounds that are the subject of this invention are conveniently prepared by reacting the appropriate amine with the appropriate acid, or corresponding acid chloride. In any event, methods for preparing compounds such as those described herein are well known to those skilled in the art of fatty acid chemistry. The details of individual preparations are listed in the following operating examples. These examples are set forth by way of lllustration and it will be understood that the invention is not to be construed as limited to these compounds or by the details therein. Analyses are in weight percent.

EXAMPLE 1 N,N-Ibis (Z-methoxyethyl ole amidei A mixture of 31.2 grams (0.23 mole) of di(2-methoxyethyl)amine, 40 grams (0.14 mole) of oleic acid, and 20 milliliters of benzene is refluxed in an apparatus equipped with a Dean-Stark trap until the evolution of water ceases.

oleamide: C, 72.18% (theory 72.43): H, 11.75% (theory 11.92) N, 3.53% (theory 3.52).

EXAMPLE 2 N,N-bis (2-ethoxyethyl palmitamide N,N-bis(2-ethoxyethyl)polmitamide is prepared by the procedure of Example 1 from 30.2 grams (0.19 mole) of di(2-ethoxyethyl)amine and 40 grams (0.16mole) palmitic acid. Analysis of the product, N,N-bis(2-ethoxyethyl)palmitamide: C,7l.8% (theory 70.34); H, 12.43% (theory 12.06); N, 3.50% (theory 3.51).

EXAMPLE 3 N,N-bis(2-ethoxyethyl)oleamide N,N-bis(2-ethoxyethyl)oleamide. is prepared by the procedure of Example 1 from 33.8 grams (0.21 mole) of di(2-ethoxyethyl)amine and 40 grams (0.14 mole) of oleic acid. Analysis of the product, N,N-bis(2-ethoxyethyl)oleamide: C, 73.37% (theory 73.31); H, '11.75% (theory 11.92); N, 3.53% (theory 3.52).

EXAMPLE 4 N,N-bis 2-ethoxyethyl) -2-ethylhexanamide This product is prepared using 30.2 gr. (0.20 mole) of di(2-ethoxyethyl)amine, 15.8 grams (0.20 mole) of pyridine dissolved in milliliters of benzene, and 30.5 grams (0.20 mole) of Z-ethylhexanoyl chloride which is added dropwise with stirring. After stirring for an additional hour the reaction mixture is filtered, washed successively with dilute hydrochloric acid and wateryand.

dried over anhydrous sodium sulfate. Free acid is removed by percolating the benzene solution through a column of activated alumina and eluting the amide with a 1:1 ethanol-benzene mixture. The solvent is then removed by stripping under reduced pressure. Analysis of the product, N,N bis(2-ethoxyethyl-Z-ethylhexanamide: C, 66.26% (theory 66.85); H, 11.65% (theory 11.56); N, 4.88% (theory 4.80).

EXAMPLE 5 N,N-bis(2-ethoxyethyl)naphthenamide N,N-bis(2-ethoxyethyl)naphthenamide is preparedby the procedure of Example 1 from 29.3 grams (0.18 mole) of di(2-ethoxyethyl)amine and 30 grams (0.14 mole) of naphthenic acid. The neutralization equivalent of the naphthenic acid is 217. The product, N,N-bis(2-ethoxyethyl)naphthenamide, has a nitrogen content of 3.90% (theory 3.89).

EXAMPLE 6 Ethyl 2,2-dimethyl-3 [di(2-methoxyethyl)amino] carbonylcyclobutaneacetate This material is prepared by the procedure of Example 4 from 17.2 grams (0.13 mole) of di(2-methoxyethyl) amine, 30 grams (0.13 mole) of ethyl'2,2-dimethyl-3- chlorocarbonylcyclobutaneacetate, and 10.2 grams (0.13 mole) of pyridine. Analysis of the product, ethyl 2,2-dimethyl- 3[di(2 methoxyethyl)amino]carbonylcyclobutaneacetate: C, 61.15% (theory 62.01); H, 9.56% (theory 9.50); N, 4.09% (theory 4.25).

EXAMPLE 7 j N,N-bis(2-methoxyethyl)amide of selectively hydrogenated cottonseed oil fatty acids N,N-bis(2-methoxyethyl)amide' of selectively hydrogenated cottonseed oil fatty acids are prepared by the.

procedure of Example 1 from 25.5 grams (0.19 mole) of'di(Z-methOXyethyDamine'and 35 grams (0.12 mole) of selectively hydrogenated cottonseed oil fatty acids. (The selectively hydrogenated cottonseed oil fatty acids have an iodine value of 73.2, a thiocyanogen value of 68.0, and a neutralization equivalent of 274'). The product, N,N-bis(2-methoxyethyl)amide of selectively hydrogenated cottonseed oil fatty acids, has a nitrogen contact EXAMPLE 8 N,N-bis(2-eth0xyethyl)amide of animal "acids EXAMPLE 9 (carbethoxymethyl) oleamide N,N-bis(carbethoxymethyl)oleamide is. prepared by the procedure of Example 4 from 18.9 grams (0.10 mole) of di(carbethoxymethyl)amine, 31.5 grams (0.10 mole) of oleoyl chloride, and 8.1 grams (0.10 mole) of pyridine. The product, N,N-bis((carhethoxymethyl)oleamide has a nitrogen content-of 2.97% (theory 3.09%). 7

EXAMPLE l N,N-bis (2-ethoxyethyl) decanamide N,N-bis(2-ethoxyethyl)decanamide is prepared by the procedure of Example 1 from 47.1 grams (0.29 mole) of di(2-ethoxyethyl)amine and 35 grams (0.20 mole) of capric acid. Analysis of the product, N,N-bis(2-ethoxyethyl)decanamide: C, 67.97% (theory 68.51; H, 11.66% (theory 11.83); N, 4.42% (theory 4.44).

EXAMPLE 1 1 N,N-bis 2ethoxyethyl) stearamide N,N-bis(2-ethoxyethyl)stearamide is prepared by the procedure of Example 1 from 29.7 grams (0.18 mole) of di(2-ethoxyethyl)amine and 35 grams (0.12 mole) of stearic acid. Analysis of the product, N,N-bis(2-ethoxyethyl)stearamide: C, 72.88% (theory 72.93); H, 12.54% (theory 12.49); N, 3.32% (theory 3.27).

EXAMPLE 12 N,N-bis(2-ethoxyethyl)erucamide N,N-'bis(2-ethoxyethyl)erucamide is prepared by the procedure of Example 1 from 28.5 grams (0.18 mole) of di(2-ethoxyethyl)amine and 40 grams (0.12 mole) of erucic acid. Analysis of the product, N,N-bis(2-ethoxyethyl)erucamide: C, 74.45% (theory 74.75); H, 12.33% (theory 12.35); N, 2.87% (theory 2.91).

6 EXAMPLE 13 N,N-bis(2-ethoxyethyl)amide of Limnanthes douglasii oil fatty acids N,N-bis(2-ethoxyethyl)amide of Limnanthes douglasii oil fatty acids is prepared by the procedure of Example 1 from 26.4 grams (0.16 mole) of di(Z-ethoxyethyl) amine and 35 grams (0.11 mole) of Limnanthes douglasii oil fatty acids. (The Limnanthes douglasii oil fatty acids has a neutralization equivalent of 320). The product N,N-bis(2-ethoxyethyl)amide of Limnanthes douglasii oil fatty acids has a nitrogen content of 3.09%.

EXAMPLE 14 N,N-N',N-tetra(2-ethoxyethyl)amide of dimer acid This material is prepared by the procedure of Example 1 from 30.1 grams (0.19 mole) of di(Z-ethoxyethyl) amine and 35 grams (0.06 mole) of dimer acid. The resulting product has a nitrogen content of 2.91%.

EXAMPLE 15 N,N-bis(2-methoxyethyl)amide of parsley seed oil fatty acids N,N-bis(2-methoxyethyl)amide of parsley seed oil fatty acids is prepared by the procedure of Example 1 from 32.6 grams (0.25 mole) of di(2-methoxyethyl)amine and 50 grams (0.16 mole) of parsley seed oil fatty acids. The resulting product has a nitrogen content of 2.99% (theory 3.22).

EXAMPLE 16 N,Nbis(2-methoxyethyl)amide of rapeseed oil fatty acids This material is prepared by the procedure of Example 1 using 32.9 grams (0.25 mole) of di(Z-methoxyethyl) amine and 50 grams (0.16 mole) of rapeseed oil fatty acids. The resulting product has a nitrogen content of 3.10% (theory 3.35).

EXAMPLE 17 N,N-bis (Z-methoxyethyl linoleamide This material is prepared by the procedure of Example 1 from- 28.5 grams (0.21 mole) of di(Z-methoxyethyl) amine and 40 grams (0.14 mole) of linoleic acid. Results of the analysis of the resulting product follow: C, 72.48% (theory 72.83); H, 11.43% (theory 11.38); N, 3.48% '(theory'3.54).

EXAMPLE 18 N,N-bis(2-ethoxyethyl) epoxystearamide N,N bis(2 ethoxyethyl)epoxystearamide is an epoxidized sample of the N,N-bis(2-ethoxyethyl)oleamide of Example 3, having an oxirane oxygen content of 3.33%.

EXAMPLE 19 N,N-bis(2-cyanoethy1) oleamide N,N bis(2 cyanoethyl)0leamide was prepared by the procedure of Example 4 from 14.3 grams (0.12 mole) of fl-pf-iminodipropionitrile, 35 grams (0.12 mole) of oleoyl chloride, and 9.2 grams (0.12 mole) of pyridine. Analysis of the resulting product gives: C, 73.69% (theory 74.36); H, 10.63% (theory 10.66); N, 10.80% (theory 10.85).

EXAMPLE 20 N,N-bis (2-cyanoethoxyethyl) oleamide Fifty grams (0.135 mole) of N,N-bis(2-hydroxyethyl) oleamide, and 5 ml. of Triton B (40% in methanol) in 5 ml. of water are dissolved in an equal volume of 1,4- dioxane. The temperature is then raised to 55 C. after which 29 grams (0.55 mole) of acrylonitrile is added drop- Wise with stirring. Stirring is then continued for about three hours after the acrylonitrile addition. While still warm the reaction mixture is poured into 800 milliliters of diethyl ether, and allowed to stand overnight. The

polyacrylonitrile is then filtered off and the filtrate washed successively with four SO-ml. portions of normal hydrochloric acid in water, dried, and stripped of solvent. The residual acidity is removed by percolation through activated alumina. The resultant product has a nitrogen content of 8.50% (theory 8.80%).

Portions of the products prepared according to Examples 1 through are then evaluated as primary, solventtype plasticizers for vinyl-type resins by the following procedures:

(1) Incorporating the plasticizer in a vinyl chloride- The formulation for each sample is then milled, molded, and then tested for: (a) tensile strength (p.s.i.); (b) 100% modulus (p.s.i.); (c) elongation (percent); (d) brittle point C); (e) volatility loss in percent; and, (f) compatibility.

The results of the above tests are then comparedlwith control results obtained when a standard plasticizer such as di 2 ethylhexylphthalate (DOP) or dioctyladipate (DOA) is used. These results are summarized in Table L! C denotes compatibility and 1 denotes incompatibility as primary plasticizers in the proportions used.

TABLE I Tensile 100% Elong- Brittle Volatility Com- Ex. strength, modulus, ation, point, less, pati- No. Plastlcizer p.s.i. p.s.i percent 0 percent bility N,N-bis(Z-methoxyethyl)olcamide 2,800 1,140 370 -53 2. 7o 0. N,N-bis(Z-ethoxyethyl)palmitamide. 2,860 1, 390 360 43 1.217 C. N,N-bis(2ethoxyethyi)palmitamida 3,050 2, 430 190 29 0.37 C. N,N-bis(2-ethoxyethyl)oleamide 2,800 1, 410 340 -57 2.01 C. N ,N-bis(2-ethoxyethyl)2'ethylhexanarnide 2, 760 1,280 320 37 8.23 C. N,N-bis(Z-ethoxyethyl)naphthenamidc 3,050 1,600 300 -21 9.58 .C. E.1yl 2,2-dimethyl-3kli(Z-methoxycthyl)amin0]carbonylcyclobutaneacetate 3,300 1,510 310 7 7.55 C.

N ,N-bis(2-methoxyethyl)amide of selectively hydrogenated cottonseed oil fatty acids 2, 630 1, 310 300 49 1. 13 C. N,Nbis(2- hoXyethyDamide of animal acids 2, 790 1,440 340 47 1. C. N,N-bis(carbethoxymethyl)oleamide 2,920 1,730 280 33 C. N N-bis(2-ethoxyethyl)decanam' e 2, 580 1,090 350- 7.33 C. N N-bis(2-ethoxyethyl)stearam1de 2,820 1, 470 360 37 0.32 C, N,N-bis(Z-ethoxyethyDerucamide 2, 480 1. 630 270 51 0.83 C. N,N-l)is(2-ethoxyethyl)amide of Li'mnanthes dong 3, 280 1, 560 330 1. 61 C. N ,N-N,N-tetra(2-ethoxyethyl)amide of dimer acid 3, 120 2,065 320 0, 43 C. N,N-bis(ZmethoXyethyDamide of parsley seed oil fatty acid 2, 910 1, 350 360 =47 1. 94 C. N,N-bis(2-methoxyethyl)amide of rapeseed oil fatty acids 2, 880 1, 440 380 =51 0. 83 G. N,N-bis(2-rnethoxyethyl)linoleamide 2,860 1, 440 350 =51 I.

N ,N-bis(Z-ethoxyethyl)epoxystearamid 2,730 1,130 360 =33 0.60 C. N,N-bis(2-cyanoethyD0leamide I. N,N-bis(2-cyanoethoxyethyl)oleam 3, 4 0 2, 390 310 I.

20 Di-2-ethylhexylphthalate (control)- 3, 050 1, 610 330 1. C.

Dioctyl adipate (control) 890 1, 380 =55 6. 00 C No'rE.Above compounds tested in vinyl-chloride-vinyl acetate eopolymer. Compound is tested in polyvinyl chloride. vinyl acetate copolymer (Vinylite VYDR) a copolymer We claim: 7 consisting of vinyl chloride and 5% vinyl acetate. 35 1. N,N-b1s(Z-ethoxyethyl)naphthenamide.

(2) Incorporating the plasticizer in a polyvinyl chloride resin (66011 0 References Cited In either method, the following standard formulation UNITED STATES PATENTS is used ercent being by weight.

p 40 3,444,197 5/1969 Youngdale 260-558 Percent Polymer (or copolymer) 63.5 Plasticizer 35.0 Stearic acid 0.5 Basic lead carbonate 1.0

Total 100.0

HENRY R. JILES, Primary Examiner HARRY I. MONTZ, Assistant Examiner 1 US. Cl. 'X.R. Y 260-29.8, 32.5, 348,404, 465.4, 475,482, 558, 561, 941' 

